Compounds and processes that generate cyclopropenes and substituted cyclopropenes on demand

ABSTRACT

Compounds and methods that release 1-methylcyclopropene, 1-trifluoromethylcyclopropene, and other substituted cyclopropenes are disclosed. The compounds and methods overcome present limitations for storage, transportation, and application of the cyclopropene containing compounds by using light, including sunlight, and/or heat as the primary release trigger. Additional products released include innocuous gases and value added aryl-group compounds.

CROSS-REFERENCE

Provisional Patent Applications covering the below described inventionwere submitted, via Express Mail, which bore label number EM 425754569US and EG 835094455 US, and were assigned application Nos. 61/341014 and61/462572. The inventors claim the priority date of said ProvisionalPatent Applications.

GOVERNMENT RIGHTS

Not Applicable.

BACKGROUND

The useful properties of plant ethylene receptor inhibitors have beenwell documented. For example, 1-methylcyclopropene (CAS #3100-04-7), asubstituted cyclopropene (hereafter, simply referred to as “1-MCP”), hasbeen demonstrated to help increase the shelf life and storagecharacteristics of many fruits and flowers.

More recently, it has been demonstrated that 1-MCP, or analoguesthereof, can be used in agricultural applications. Specifically, 1-MCP,and analogues thereof, are used to retard the ripening process inplants, which allows the plant materials to last much longer thanuntreated plants. Additionally, 1-MCP, and analogues thereof, are usedfor crop protection during times of stress that includes drought,excessive heat, and excessively low temperatures. With regard to theabove specified agricultural applications and without limitation, the1-MCP analogue compounds may be considered to be related compounds whichhave similar uses as 1-MCP in agricultural applications. The analoguesof 1-MCP with regard to the above specified agricultural applicationsinvolve compounds which contain the cyclopropene moiety. The compoundscyclopropene, 3-methylcyclopropene, 1-ethylcyclopropene,1,2-dimethylcyclopropene, 1,3-dimethylcyclopropene, and3,3-dimethylcyclopropene have similar agricultural significance, albeitthe aforementioned compounds are weaker plant ethylene receptorinhibitors in comparison to 1-MCP, and they are included amongst manyother releasable analogue compounds that are covered by this technology.Generally, these cyclopropene containing compounds are regarded as plantethylene receptor antagonist, and inhibit plant senescence andabscission in a wide variety of plant species. In particular, thecyclopropene containing analogue 1-trifluoromethylcyclopropene(hereafter, simply referred to as “1-TFMCP”) is a plant ethylenereceptor antagonist with different characteristics than 1-MCP whichinclude slightly increased water solubility and increased penetrationthrough waxy or otherwise lipophilic layers of some plant species.

Unfortunately, 1-MCP and 1-TFMCP are highly unstable gases, and socannot be conventionally applied, or easily stored for long periods oftime. Presently, the only commercially available forms of 1-MCP are inhighly dilute mixtures and 1-TFMCP is not commercially available. Forthe foregoing reasons, there is a need for a solution to the problemsassociated with the shelf-life, long term storage, transport, andrelease of 1-MCP, 1-TFMCP, and additional cyclopropene containinganalogues.

SUMMARY

The above listed applicants have identified a solution to the problemsassociated with the shelf-life, long term storage, transport, andrelease of 1-MCP, 1-TFMCP, and analogues thereof, on an as needed basisby covalently linking 1-MCP, 1-TFMCP, or analogues thereof, directly toa molecular compound which, upon activation, releases the compound1-methylcyclopropene, 1-TFMCP, or analogues thereof. Additionally, somecompounds that are used in this manner to release 1-MCP may be furtherstabilized via a reversible reaction forming a ketal (as an asymmetricortho-ester), which only requires exposure to a mildly acidic aqueoussolution to afford deprotection, thereby yielding the immediate lightand/or heat active precursor compound and either a diol or twoequivalents of an alcohol. The light and/or heat active precursor maythen yield the cyclopropene or substituted cyclopropene (such as 1-MCP,1-TFMCP, etc.) upon further exposure to light and/or heat. Thistechnology allows for formulations that include solid mixtures, aqueoussolutions, non-aqueous solutions, colloidal dispersions, or directapplication of the release vent such that the 1-MCP Release System canbe conventionally applied, which is then activated by light and/or heatto release the 1-MCP, 1-TFMCP, or analogue thereof.

DRAWINGS

These and other features, aspects and advantages of the presentinvention will become better understood with reference to the followingdescription, appended claims and accompanying drawings where:

FIG. 1 shows the general light and/or heat driven release mechanismcontemplated herein;

FIG. 2 shows the general stereochemistry of2-oxa-bicyclo[2.1.0]penta-3-one;

FIG. 3 shows the general stereochemistry of3,4-dioxa-bicyclo[4.1.0]hepta-2,5-dione;

FIG. 4 shows the manner by which 3,4-dioxa-bicyclo[4.1.0]hepta-2,5-dionemay proceed through a stable intermediate comprising2-oxa-bicyclo[2.1.0]penta-3-one in a multi-step reaction schemeultimately resulting in the generation of 1-MCP or analogues thereoffrom 3,4-dioxa-bicyclo[4.1.0]hepta-2,5-dione; and

FIG. 5 shows some possibilities of value added aryl-unit containingproducts that may be created from different configurations of Compound4.

DESCRIPTION

The strategies discussed herein pertaining to the capture and release,and to release without capture of 1-MCP, 1-TFMCP, and analogues thereof,are based upon light and/or heat driven release mechanisms. When thecovalently linked system is exposed to light and/or heat, 1-MCP,1-TFMCP, or analogue thereof, is released along with the linkedmolecule. The release system formulations include one, or more, of such1-MCP, 1-TFMCP, or other analogue releasing compounds, and in variousproportions or mixtures thereof. Here, the term mixtures includes, butis not limited to, combinations of compounds within a given method(described herein), combinations of compounds spanning one or moremethods (described herein), combinations of stereo-isomers, where theyexist, and all permutations thereof, and also where any of the methodscontained herein are used in combination with a different method in thegeneral field of practice.

In addition to light, heat may also be used to generate the desired1-MCP, 1-TFMCP, or related analogue in some cases. Thus, light, heat, orcombinations of light and heat may be used in these reactions togenerate the desired compounds. The amount of heat and/or light energyrequired for the release of 1-MCP, 1-TFMCP, or analogues thereof, isdependent upon the specific precursor compound and the specificformulation in which it is contained, amongst other determinants. Thus,the heat and light energy requirements for the release of 1-MCP,1-TFMCP, or analogues thereof, can be attenuated to meet a desiredrelease profile. Specific compounds more generally represented byMarkush Structures of Compounds 1 through 8 can be obtained such thatvery high thermal stability is imparted, but a low light energythreshold is obtained. In the aforementioned example, the compound willexhibit long shelf life, even at high temperatures, so long as exposurelight is avoided during storage. Upon exposure to light, the 1-MCP,1-TFMCP, or analogue thereof is released.

Some of the precursor compounds (such as Compound 1) used to generate1-MCP, 1-TFMCP, or analogues thereof, may be further stabilized as theirrespective ketal (as an asymmetric ortho-ester), which affords increasedstability to heat and/or light. Upon exposure of such compounds toacidic aqueous solutions under mild conditions, the immediate precursoris generated along with the respective diol or two equivalents of analcohol containing compound. The immediate precursor will then yield1-MCP, 1-TFMCP, or analogues thereof, and carbon dioxide upon furtherexposure to heat and/or light.

Without limitation, the 1-MCP Release System more fully set forth belowis comprised of a precursor molecule (Compound 1 through 8), which uponactivation to an excited state, generates 1-MCP, 1-TFMCP, or analoguethereof, and one or more by-products. The by-product(s) may consist ofone or more gases. In addition, the by-product(s) may also entail therelease of an additional molecule which contains an aryl group. The arylgroup released may be, by design, a “value added material.” By way ofexample and without limitation, such value added material(s) may be apesticide (such as a herbicide, insecticide, fungicide, rodenticide,and/or acaracide), herbicide, bee attractant, or preservative.

To date the below identified molecules and protocols have beenidentified as addressing the problems associated with the capture andrelease, and release without capture of 1 -MCP, 1-TFMCP, or analoguesthereof. These aforementioned molecules are referred to as Compounds 1through 8, and the aforementioned methods are referred to as Methods 1through 4 in the context of this patent application.

The 1-MCP and analogues thereof, may be described as two general sets ofreaction products which contain a cyclopropene moiety. These two productsets can be represented as Product 1 or Product 2, below, with respectto the methods detailed more fully herein.

Where R₁ or R₄ of Product 1 is comprised of a methyl group (—CH₃), andall other R₁ through R₄ are hydrogens, Product 1 will be 1-MCP, below.Where R₁ or R₃ of Product 2 is comprised of a methyl group (-CH₃), andall other R₁ through R₄ are hydrogens, Product 2 will be 1-MCP, below.Where R₁ or R₄ of Product 1 is comprised of a tri-fluoromethyl group(—CF₃), and all other R₁ through R₄ are hydrogens, Product 1 will be1-TFMCP, below. Where R₁ or R₃ of Product 2 is comprised of atri-fluoromethyl group (—CF₃), and all other R₁ through R₄ arehydrogens, Product 2 will be 1-TFMCP, below.

Compound 1: Analogues of 2-oxa-bicyclo[2.1.0]penta-3-one

Compound 1 (analogues of cyclopropane annulated beta-lactone), which mayalso be referred to as analogues of 2-oxa-bicyclo[2.1.0]penta-3-one,below, has been found to be reactive in strategies to generate 1-MCP,and analogues thereof, by heat and/or light.

The general stereochemistry of Compound 1 may be more clearly seen inFIG. 2, where A and B represent the two general enantiomers of Compound1, where they exist.

The general reaction of Compound 1 upon exposure to light and/or heat,depending on the composition of the identified R groups, yields Product1, above, where the R groups of Product 1 correspond to the samesubstituents on Compound 1, and one equivalent of carbon dioxide.Sunlight, or artificial light sources may be used. Increased rates maybe obtained by using sonication (ultrasound) and/or a LASER as thesource of light and/or in conjunction with a photo-catalyst, such as onecomprising palladium. The product entailing Product 1 in this case willgenerally be an achiral product or a racemic mixture where they exist.It is possible to obtain a non-racemic product composition by thismethod under certain conditions, such as when the light source ispolarized.

The R groups for Compound 1 may, independently for each respective R₁through R₄, be comprised of a hydrogen (—H), chlorine (—Cl), or fluorine(—F) atom, or group comprised of methyl (—CH₃), ethyl (—CH₂CH₃),ethylene (—CHCH₂), ethyne (—CCH), n-propyl (—CH₂CH₂CH₃), iso-propyl(—CH(CH₃)₂), cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃), propene(—CHCHCH₃ or —CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂), propyne(—CCCH₃ or —CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH),ethylalcohol (—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)),propanol (—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F) perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl).

The products of 1-MCP and carbon dioxide may be obtained from eitherenantiomer of Compound 1 when R₁ or R₄ is a methyl group and all other Rgroups are hydrogen. The products of 1-TFMCP and carbon dioxide may beobtained from either enatiomer of Compound 1 when R₁ or R₄ is atrifluoromethyl group and all other R groups are hydrogen.

Compound 2: Analogues of 2-oxa-bicyclo[2.1.0]penta-3-one ketal

The Compound 1 may be generated via a reversible reaction from itsrespective analogue ketal (an asymmetric ortho-ester), identified belowas Compound 2 (analogues of 2-oxa-bicyclo[2.1.0]penta-3-one ketal).Here, the R₁, R₂, R₃, and R₄ groups may be independently comprised ofany of the R groups discussed above for Compound 1. The R₅ and R₆ groupsmay share a covalent bond (shown as a dashed line, below) or may be twoindependent subunits. Independently, for R₅ and R₆, they may becomprised of a methyl (—CH₃), ethyl (—CH₂CH₃), or propyl (—CH₂CH₂CH₃)groups. Where R₅ and R₆ share a covalent bond, R₅ and R₆ together may bean ethyl (—CH₂CH₂—) or propyl (—CH(CH₃)CH₂—) group.

A general reaction to form the ketal protected variant of Compound 1 (asan asymmetric ortho-ester; Compound 2), utilizes the light initiated[2+2] reaction of Product 1 (now, as a reactant) with a dimethylcarbonate, diethyl carbonate, ethylene carbonate, or propylenecarbonate. The reaction can be carried out in a wide variety of solventmedia (excepting acidic aqueous solutions), or under vacuum conditionsfor the gas-phase reaction. The use of the above molecules in aphoto-induced [2+2] reaction yields Compound 2, where R₅ and R₆ are bothmethyl (—CH₃) or ethyl (—CH₂CH₃) for the case where dimethyl carbonate,or diethyl carbonate are used, respectively, and yields Compound 2 whereR₅ and R₆ share an ethylene bridge (—CH₂CH₂—) for the case that ethylenecarbonate is used, or share a methyl substituted ethylene bridge(—CH(CH₃)CH₂—) for the case that propylene carbonate is used.

When R₁ or R₄ is a methyl group on Product 1 (1-MCP), and all other Rgroups are hydrogens, 1-MCP may be sequestered by a photo-induced [2+2]reaction with the aforementioned carbonates. Such a reaction yieldsCompound 2 where R₁ is a methyl group and R₂, R₃, and R₄ are hydrogens,or Compound 2 where R₄ is a methyl group and R₁, R₂, and R₃ arehydrogens. When R₁ or R₄ is a trifluoromethyl group on Product 1(1-TFMCP), and all other R groups are hydrogens, 1-TFMCP may besequestered by a photo-induced [2+2] reaction with the aforementionedcarbonates. Such a reaction yields Compound 2 where R₁ is atrifluoromethyl group and R₂, R₃, and R₄ are hydrogens, or Compound 2where R₄ is a trifluoromethyl group and R₁, R₂, and R₃ are hydrogens.

Upon exposure of Compound 2 to excess water in the presence of H⁺ (anaqueous acidic solution), the following respective alcohol or diol (asProduct 3, below) and Compound 1 are generated under mild conditions.

Compound 3: Analogues of 3,4-dioxa-bicyclo[4.1.0]hepta-2,5-dione

Another important molecule is Compound 3 below, (analogues of3,4-dioxa-bicyclo[4.1.0]hepta-2,5-dione). Here, the R₁, R₂, R₃, and R₄groups may be independently comprised of any of the R groups discussedabove for Compound 1.

The general stereochemistry for Compound 3 is illustrated in FIG. 3,where A and B represent the two general stereoisomers. Both enantiomersof Compound 3, where they exist, are active in generating Product 1.

The general reaction for Compound 3 to produce cyclopropenes andsubstituted cyclopropenes (as Product 1, above) requires the exposure ofCompound 3 to light and/or heat and generates products consisting ofProduct 1, where R₁ through R₄ of Compound 3 correspond to R₁ through R₄of Product 1, and two equivalents of carbon dioxide. Sunlight, orartificial light sources may be used. Increased rates may be obtained byusing sonication (ultrasound) and/or a LASER as the source of lightand/or a light source in conjunction with a photo-catalyst, such as onecomprising palladium.

For the case that 1-MCP is to be generated from Compound 3, R₁ or R₄ iscomprised of a methyl group and all other R groups are hydrogens andupon exposure to light and/or heat 1-MCP and two equivalents of CO₂ areproduced. For the case that 1-TFMCP is to be generated from Compound 3,R₁ or R₄ is comprised of a trifluoromethyl group and all other R groupsare hydrogens and upon exposure to light and/or heat 1-TFMCP and twoequivalents of CO₂ are produced.

In addition, when subject to light and/or heat Compound 3 may proceedthrough a stable intermediate comprising Compound 1 in a multi-stepreaction scheme ultimately resulting in the generation of 1-MCP oranalogues thereof (Product 1) from Compound 3 as illustrated in FIG. 4.

Compound 4: Analogues oftetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-one

Another important molecule is Compound 4, below, (analogues oftetracyclo[5.2.1.0^(2,6). 0^(3,5)]deca-8-en-10-one).

Here, the R₁ or R₄ must be comprised of a methyl group (—CH₃), or atrifluoromethyl group (—CF₃) and all other R₁ through R₄ are protons(—H). Both the R₁ and R₄ groups of Compound 4 are in an eclipsed (cis)conformation, as are the R₅ and R₁₀ groups. The R₅ through R₁₀ groupsmay, independently, be comprised of any of the groups discussed, above,for Compound 1. Additionally, any of the R₅ through R₁₀ groups may,independently, be comprised of a phenyl (—C6H5), a sodium phenoxide(—C6H4ONa), or a substituted phenyl group where the substituents (fivetotal substituents including protons) on the phenyl group may be any ofthe groups discussed above for Compound 1. It is preferable that atleast one of R₅ through R₁₀ be comprised of something other thanhydrogen.

There are several analogues of Compound 4, which may be represented bythe Markush Structures, below, where the primary difference between therespective compounds pertains to their endo, and/or exo orientations.These orientations are (endo, endo), (endo, exo), (exo, exo), and (exo,endo) for the parent tetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-onecompounds, below, Compound 4A, Compound 4B, Compound 4C, and Compound4D, respectively, where bond angles have been distorted for labelingpurposes. Due to steric hindrance effects, Compound 4B and Compound 4Dgenerally exhibit greater stability than Compound 4A and Compound 4C,but any of the isomers and stereoisomers of Compounds 4A through 4D aresuitable for producing Product 1 upon exposure to light or to light andheat.

When Compound 4 is exposed to light or light and heat it yields oneequivalent each of carbon monoxide, Product 1 as 1-MCP (if R₁ or R₄ is amethyl group) or 1-TFMCP (if R₁ or R₄ is a trifluoromethyl group), andProduct 4 (below). Sunlight or artificial light sources may be used.Increased rates may be obtained by using sonication (ultrasound) and/ora LASER as the source of light and/or a light source in conjunction witha photo-catalyst, such as one comprising palladium.

For the case where any one of R₅, R₆, R₇, R₈, R₉, or R₁₀ is a methylester (and all remaining R groups are protons) the light activatedreleased compounds will be carbon monoxide, and either 1-MCP (where R₁or R₄ is a methyl group) or 1-TFMCP (where R₁ or R₄ is a trifluoromethylgroup), and methylbenzoate as Product 4 (a common bee attractant).

Similarly, amongst other possibilities, the aromatic system can bechosen to be a fungicide, preservative agent, or insect repellant as isthe case for the released aromatic compounds depicted in FIG. 4. Thelist of potential “value added” aryl-unit containing products (asProduct 4) afforded by Compound 4 are numerous. Many common pesticides(including herbicides, insecticides, fungicides, rodenticides, and/oracaracides, by way of example), bee attractant, preservative and otheragrichemical compounds have been identified that are potential “valueadded” side products (as Product 4) of Compound 4 concomitant with therelease of 1-MCP or 1-TFMCP.

Compound 5: Analogues of tricyclo[3.2.2.0^(2,4)]nona-6,8-diene

Another important molecule is Compound 5, below, (analogues oftricyclo[3.2.2.0^(2,4)]nona-6,8-diene), where bond angles are showndistorted for labeling purposes (R₁ and R₄ are in an eclipsed (cis)conformation).

Here, the convention of using “w” and “x” components represent theadjacent carbon atoms of the general substituents containing an ethylenebridge or aromatic ring which may or may not contain a silyl diether; A,B and C, respectively, below, where dashed lines (on A, B, and C) areused to indicate the covalent bonds to the bridgehead carbons ofCompound 5 (indicated with arrows “a” and “b” for “w” and “x”,respectively). The “y” and “z” components, likewise represent theadjacent carbon atoms of the same general substituents A, B and C, where“y” replaces “w” and “z” replaces “x” in each of A, B, and C, and theyare now denoted as A′, B′ and C′ and their corresponding R groups arenow denoted as R_(n)′. In this manner, the six (non-equivalent) generalpermutations for Compound 5 can be expressed as AA′, AB′, AC′, BB′, BC′,and CC′.

As an example, the Compound represented by 5AB′ is shown below, wherethe w, x, y, and z labels have been removed.

Here, the R₁ or R₄ must be comprised of a methyl group (—CH₃), or atrifluoromethyl group (—CF₃) and all other R₁ through R₄ are protons(—H). All other R and R′ groups of Compound 5 may be comprised of any ofthe substituents under Compound 1.

When Compound 5 is exposed to heat, one equivalent each of Product 1 andProduct 5, below, are yielded. Where R₁ or R₄ is a methyl group (—CH₃)and all other R₁ through R₄ are hydrogens, the Product 1 component willbe 1-MCP. Where R₁ or R₄ is a trifluoromethyl group (—CF₃) and all otherR₁ through R₄ are hydrogen, the Product 5 component will be 1-TFMCP.Akin to the Compound 4 and analogues thereof, all R groups beyond R₁through R₄ should be chosen to entail the release of a benign orbeneficial compound containing an aromatic moiety (instead of benzene,in the case of Compound 5AA′). Again, the list of potential“value-added” compounds is quite large. Where Compound 5AA′ is used, andany one of R₅, R₆, R₇, R₈, R₇′, or R₈′ is comprised of a methyl estergroup, and all other R₅ through R₈′ are hydrogens, the yielded productwill contain (as Product 5AA′) a methylbenzoate (a common beeattractant). Sonication (ultrasound) can be used to increase rates.

Method 1. Release of 1-MCP via Exposure of 2(5H)-furanone &2(3H)-furanone and Analogues Thereof to Light

Under Method 1, Compound 6 (analogues of 2(5H)-furanone) and Compound 7(analogues of 2(3H)-furanone), below, may be used to convey the generalcompounds that when exposed to light and/or heat release 1-MCP, oranalogues thereof, as Product 1 and/or Product 2 in addition to oneequivalent of carbon dioxide. The reaction pathway may involve a protonmigration and bond shift such that Product 1 or Product 2 may beproduced, depending upon the substituents (and wavelength of lightutilized). The intermediate in this reaction is thought to involveCompound 1. Where Product 1 or Product 2 is to be comprised of 1-MCP, itis preferable that for both Compound 6 and Compound 7, R₃ or R₄ iscomprised of a methyl group, and all other R are protons. Where Product1 or Product 2 is to be comprised of 1-TFMCP, it is preferable that forboth Compound 6 and Compound 7, R₃ or R₄ is comprised of atrifluoromethyl group, and all other R are protons. It is also preferredthat the solution media used (if any) be transparent with a low cut-offabsorption. Sunlight or artificial light sources may be used. Increasedrates may be obtained by using sonication (ultrasound) and/or a LASER asthe source of light and/or a light source in conjunction with aphoto-catalyst, such as one comprising palladium.

Each R group for Compound 6 and Compound 7 may be comprised of any ofthe R groups discussed for Compound 1.

When exposed to light in the ultra-violet Compound 6 yields oneequivalent of product comprised of Product 1 and/or Product 2 and oneequivalent of carbon dioxide. When exposed to light in the ultravioletrange Compound 7 yields one equivalent of product comprised of Product 1and/or Product 2, and one equivalent of carbon dioxide. Where R₄ or R₃of Compound 6 is comprised of a methyl group and all other R areprotons, Compound 6 yields one equivalent of 1-MCP (as Product 1 orProduct 2) and one equivalent of carbon dioxide under ideal conditionswhen exposed to a light source. Where R₄ or R₃ of Compound 6 iscomprised of a trifluoro-methyl group and all other R are protons,Compound 6 yields one equivalent of 1-TFMCP (as Product 1 or Product 2)and one equivalent of carbon dioxide under ideal conditions when exposedto a light source.

Where R₄ or R₃ of Compound 7 is comprised of a methyl group and allother R are protons, Compound 7 yields one equivalent of 1-MCP (asProduct 1 or Product 2) and one equivalent of carbon dioxide under idealconditions when exposed to a light source. Where R₄ or R₃ of Compound 7is comprised of a trifluoromethyl group and all other R are protons,Compound 7 yields one equivalent of 1-TFMCP (as Product 1 or Product 2)and one equivalent of carbon dioxide under ideal conditions when exposedto a light source.

Sunlight or artificial light sources may be used. Increased rates may beobtained by using sonication (ultrasound) and/or a LASER as the sourceof light and/or a light source in conjunction with a photo-catalyst,such as one comprising palladium.

Method 2: Release of 1-MCP via Exposure of Analogues of3-oxabicyclo[3.1.0]hexane-2,4-dione to Light

Under Method 2, Compound 8 (analogues of3-oxabicyclo[3.1.0]hexane-2,4-dione), below, may be used to convey thegeneral compounds that when exposed to light release 1-MCP, or analoguesthereof. Compound 8, when exposed to light, yields one equivalent eachof Product 1, carbon dioxide, and carbon monoxide. For the case that R₁or R₄ are comprised of a methyl group and all other R are protons inCompound 8, the yielded products will be one equivalent each of 1-MCP(as Product 1), carbon dioxide, and carbon monoxide. For the case thatR₁ or R₄ are comprised of a trifluoromethyl group and all other R areprotons in Compound 8, the yielded products will be one equivalent eachof 1-TFMCP (as Product 1), carbon dioxide, and carbon monoxide.

Sunlight or artificial light sources may be used, but it is preferredthat a high intensity light source in the ultraviolet range be used.Increased rates may be obtained by using sonication (ultrasound) and/ora LASER as the source of light and/or a light source in conjunction witha photo-catalyst, such as one comprising palladium.

Each of the R groups identified for Method 2 may be comprised,independently for each, of any of the groups discussed for Compound 1.

Method 3: Release of 1-MCP and a Value Added Compound via Exposure ofAnalogues of tetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-one to Lightor Light and Heat

The representative parent compound for Method 3 which releases 1 -MCP(as Product 1), carbon monoxide, and an Aromatic functionalitycontaining by-product (as Product 4) may be illustrated by Compound 4and its analogues identified above where R₁ or R₄ are comprised of amethyl group and all other R, through R₄ are protons. The representativeparent compound for Method 3 which releases 1-TFMCP (as Product 1),carbon monoxide, and an Aromatic functionality containing by-product (asProduct 4) may be illustrated by Compound 4 and its analogues identifiedabove where R₁ or R₄ are comprised of a trifluoromethyl group and allother R₁ through R₄ are protons. The general reaction of Compound 4 uponexposure to light or to light and heat is one equivalent each of carbonmonoxide, Product 1, and Product 4. Where any one of R₅ through R₁₀ arecomprised of a methylester group and all other R₅ through R₁₀ areprotons, the Product 4 component will be methylbenzoate (a common beeattractant). All other R, besides R₁ through R₄ may be any of thesubstituents discussed for Compound 1, above. Again, there are severalanalogues of the parent compound, which may be represented by Compounds4A, 4B, 4C, and 4D, above, where the primary difference between therespective compounds pertains to their endo, and/or exo orientations.

The general reaction involving Compound 4 begins with a loss of carbonmonoxide concomitant with bond shift and bond cleavage resulting in theloss of carbon monoxide, which may be initiated by either heat or light.The second reaction step entails a retro[2+2] reaction to form Product 1and Product 4, which is initiated by light absorbance, and is driven bythe formation of an aromatic Product 4. Sunlight or artificial lightsources may be used. Increased rates may be obtained by using sonication(ultrasound) and/or a LASER as the source of light and/or a light sourcein conjunction with a photo-catalyst, such as one comprising palladium.

With respect to Product 4, proper substitution at positions R₅ throughR₁₀ can lead to the release of benign, or even of beneficial compounds.By way of example and without limitation, the aromatic system can bechosen to be a fungicide, preservative agent, or insect repellant as isthe case for the released aromatic compounds depicted in FIG. 4. Thelist of potential “value added” aryl-unit containing products (Product4) afforded by Compound 4 are numerous. Many common pesticides(including herbicides, insecticides, fungicides, rodenticides, and/oracaracides, by way of example), bee attractant, preservative and otheragrichemical compounds have been identified that are potential “valueadded” side products (as Product 4) of Compound 4 concomitant with therelease of 1-MCP or 1-TFMCP.

Method 4: Release of 1-MCP and a Value Added Compound via Exposure ofAnalogues of tricyclo[3.2.2.0^(2,4)]nona-6,8-diene to Heat

The representative parent compound for Method 4 which upon exposure toheat releases 1-MCP (as Product 1), and an Aromatic functionalitycontaining by-product (as Product 5) may be illustrated by Compound 5and its analogues identified above where R₁ or R₄ are comprised of amethyl group and all other R₁ through R₄ are protons. The representativeparent compound for Method 4 which upon exposure to heat releases1-TFMCP (as Product 1), and an Aromatic functionality containingby-product (as Product 5) may be illustrated by Compound 5 and itsanalogues identified above where R₁ or R₄ are comprised of atrifluoromethyl group and all other R₁ through R₄ are protons. WhereCompound 5AA′ is used, and any one of R₅, R₆, R₇, R₈, R₇′, or R₈′ iscomprised of a methyl ester group, and all other R₅ through R₈′ arehydrogens, the yielded product will contain (as Product 5AA′) amethylbenzoate (a common bee attractant). Sonication (ultrasound) can beused to increase rates. The general reaction of Compound 5 upon exposureto heat is the release of one equivalent each of Product 1 and Product5. Furthermore, as outlined above each R, excepting R_(I) through R₄, asubstituent as discussed for Compound 1, above. Increased rates may beobtained by using sonication (ultrasound).

Akin to the Compound 4, and analogues thereof, R besides R₁ through R₄,should be chosen to entail the release of a benign or beneficialcompound containing an aromatic moiety as Product 5 (instead ofbenzene). Again, the list of potential “value-added” compounds is quitelarge.

It will be understood that various changes can be made in the formdetails, arrangement, and proportions of the various parts withoutdeparting from the spirit and scope of the present invention.

1. A compound of the formula:

wherein: R₁ is hydrogen (—H), chlorine (—Cl), or fluorine (—F) atom, orgroup comprised of methyl (—CH₃), ethyl (—CH₂CH₃), ethylene (—CHCH₂),ethyne (—CCH), n-propyl (—CH₂CH₂CH₃), iso-propyl (—CH(CH₃)₂),cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃), propene (—CHCHCH₃ or—CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂), propyne (—CCCH₃ or—CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH), ethylalcohol(—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)), propanol(—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F) perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl); R₂ is hydrogen (—H), chlorine (—Cl), orfluorine (—F) atom, or group comprised of methyl (—CH₃), ethyl(—CH₂CH₃), ethylene (—CHCH₂), ethyne (—CCH), n-propyl (—CH₂CH₂CH₃),iso-propyl (—CH(CH₃)₂), cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃),propene (—CHCHCH₃ or —CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂),propyne (—CCCH₃ or —CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH),ethylalcohol (—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)),propanol (—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F) perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl); R₃ is hydrogen (—H), chlorine (—Cl), orfluorine (—F) atom, or group comprised of methyl (—CH₃), ethyl(—CH₂CH₃), ethylene (—CHCH₂), ethyne (—CCH), n-propyl (—CH₂CH₂CH₃),iso-propyl (—CH(CH₃)₂), cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃),propene (—CHCHCH₃ or —CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂),propyne (—CCCH₃ or —CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH),ethylalcohol (—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)),propanol (—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F) perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl); and R₄ is hydrogen (—H), chlorine (—Cl), orfluorine (—F) atom, or group comprised of methyl (—CH₃), ethyl(—CH₂CH₃), ethylene (—CHCH₂), ethyne (—CCH), n-propyl (—CH₂CH₂CH₃),iso-propyl (—CH(CH₃)₂), cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃),propene (—CHCHCH₃ or —CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂),propyne (—CCCH₃ or —CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH),ethylalcohol (—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)),propanol (—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F), perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl).
 2. A compound of the formula:

wherein: R₁ is hydrogen (—H), chlorine (—Cl), or fluorine (—F) atom, orgroup comprised of methyl (—CH₃), ethyl (—CH₂CH₃), ethylene (—CHCH₂),ethyne (—CCH), n-propyl (—CH₂CH₂CH₃), iso-propyl (—CH(CH₃)₂),cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃), propene (—CHCHCH₃ or—CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂), propyne (—CCCH₃ or—CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH), ethylalcohol(—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)), propanol(—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F), perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl); R₂ is hydrogen (—H), chlorine (—Cl), orfluorine (—F) atom, or group comprised of methyl (—CH₃), ethyl(—CH₂CH₃), ethylene (—CHCH₂), ethyne (—CCH), n-propyl (—CH₂CH₂CH₃),iso-propyl (—CH(CH₃)₂), cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃),propene (—CHCHCH₃ or —CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂),propyne (—CCCH₃ or —CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH),ethylalcohol (—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)),propanol (—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F), perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or -CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl); R₃ is hydrogen (—H), chlorine (—Cl), orfluorine (—F) atom, or group comprised of methyl (—CH₃), ethyl(—CH₂CH₃), ethylene (—CHCH₂), ethyne (—CCH), n-propyl (—CH₂CH₂CH₃),iso-propyl (—CH(CH₃)₂), cyclopropyl (—CH(CH₂)₂), tert-butyl(_(-C)(_(CH3))₃), propene (—CHCHCH₃ or —CH₂CHCH₂), cyclopropene(—CH(CH)₂ or —C(CH)CH₂), propyne (—CCCH₃ or —CH₂CCH), hydroxyl (—OH),methylalcohol (—CH₂OH), ethylalcohol (—CH₂CH₂OH or —CH(OH)CH₃),ethyldiol (—CH(OH)CH₂(OH)), propanol (—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or—CH₂CH₂CH₂OH), propandiol (—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or—CH₂CH(OH)CH₂OH), methylether (—OCH₃), ethylether (—OCH₂CH₃),fluoromethyl (—CH₂F), difluoromethyl (—CHF₂), trifluoromethyl (—CF₃),fluoroethyl (—CFHCH₃ or —CH₂CH₂F), perfluoroethyl (—CF₂CF₃),fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or —CH₂CH₂CH₂F), perfluoropropyl(—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl (—CH₂Cl), dichloromethyl(—CHCl₂), trichloromethyl (—CCl₃), chloroethyl (—CClHCH₃ or —CH₂CH₂Cl),perchloroethyl (—CCl₂CCl₃), chloropropyl (—CHClCH₂CH₃ or —CH₂CHClCH₃ or—CH₂CH₂CH₂Cl), perchloropropyl (—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano(—CN), aldehyde (—C(O)H), carboxylic acid (—C(O)OH), carboxylate(—C(O)O⁻), carbomethoxy (—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃),dimethyl amine (—N(CH₃)₂), or acid chloride (—C(O)Cl); R₄ is hydrogen(—H), chlorine (—Cl), or fluorine (—F) atom, or group comprised ofmethyl (—CH₃), ethyl (—CH₂CH₃), ethylene (—CHCH₂), ethyne (—CCH),n-propyl (—CH₂CH₂CH₃), iso-propyl (—CH(CH₃)₂), cyclopropyl (—CH(CH₂)₂),tert-butyl (—C(CH₃)₃), propene (—CHCHCH₃ or —CH₂CHCH₂), cyclopropene(—CH(CH)₂ or —C(CH)CH₂), propyne (—CCCH₃ or —CH₂CCH), hydroxyl (—OH),methylalcohol (—CH₂OH), ethylalcohol (—CH₂CH₂OH or —CH(OH)CH₃),ethyldiol (—CH(OH)CH₂(OH)), propanol (—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or—CH₂CH₂CH₂OH), propandiol (—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or—CH₂CH(OH)CH₂OH), methylether (—OCH₃), ethylether (—OCH₂CH₃),fluoromethyl (—CH₂F), difluoromethyl (—CHF₂), trifluoromethyl (—CF₃),fluoroethyl (—CFHCH₃ or —CH₂CH₂F), perfluoroethyl (—CF₂CF₃),fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or —CH₂CH₂CH₂F), perfluoropropyl(—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl (—CH₂Cl), dichloromethyl(—CHCl₂), trichloromethyl (—CCl₃), chloroethyl (—CClHCH₃ or —CH₂CH₂Cl),perchloroethyl (—CCl₂CCl₃), chloropropyl (—CHClCH₂CH₃ or —CH₂CHClCH₃ or-CH₂CH₂CH₂Cl), perchloropropyl (—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano(—CN), aldehyde (—C(O)H), carboxylic acid (—C(O)OH), carboxylate(—C(O)O⁻), carbomethoxy (—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃),dimethyl amine (—N(CH₃)₂), or acid chloride (—C(O)Cl); R₅ is methyl(—CH₃), ethyl (—CH₂CH₃), propyl (—CH₂CH₂CH₃), or methylene (—CH₂—), ormethylethylene (—CH(CH₃)—); and R₆ is methyl (—CH₃), ethyl (—CH₂CH₃),propyl (—CH₂CH₂CH₃), methylene (—CH₂—), or methylethylene (—CH(CH₃)—).3. A compound of the formula:

wherein: R₁ is hydrogen (—H), chlorine (—Cl), or fluorine (—F) atom, orgroup comprised of methyl (—CH₃), ethyl (—CH₂CH₃), ethylene (—CHCH₂),ethyne (—CCH), n-propyl (—CH₂CH₂CH₃), iso-propyl (—CH(CH₃)₂),cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃), propene (—CHCHCH₃ or—CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂), propyne (—CCCH₃ or—CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH), ethylalcohol(—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)), propanol(—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F), perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl); R₂ is hydrogen (—H), chlorine (—Cl), orfluorine (—F) atom, or group comprised of methyl (—CH₃), ethyl(—CH₂CH₃), ethylene (—CHCH₂), ethyne (—CCH), n-propyl (—CH₂CH₂CH₃),iso-propyl (—CH(CH₃)₂), cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃),propene (—CHCHCH₃ or —CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂),propyne (—CCCH₃ or —CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH),ethylalcohol (—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)),propanol (—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F), perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl); R₃ is hydrogen (—H), chlorine (—Cl), orfluorine (—F) atom, or group comprised of methyl (—CH₃), ethyl(—CH₂CH₃), ethylene (—CHCH₂), ethyne (—CCH), n-propyl (—CH₂CH₂CH₃),iso-propyl (—CH(CH₃)₂), cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃),propene (—CHCHCH₃ or —CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂),propyne (—CCCH₃ or —CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH),ethylalcohol (—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)),propanol (—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F), perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl); and R₄ is hydrogen (—H), chlorine (—Cl), orfluorine (—F) atom, or group comprised of methyl (—CH₃), ethyl(—CH₂CH₃), ethylene (—CHCH₂), ethyne (—CCH), n-propyl (—CH₂CH₂CH₃),iso-propyl (—CH(CH₃)₂), cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃),propene (—CHCHCH₃ or —CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂),propyne (—CCCH₃ or —CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH),ethylalcohol (—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)),propanol (—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F), perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl).
 4. A compound of the formula:

wherein: R₁ is hydrogen (—H), methyl (—CH₃), or trifluoromethyl (—CF₃);R₂ is hydrogen; R₃ is hydrogen; R₄ is hydrogen, or methyl (—CH₃)provided that R₁ is hydrogen, or trifluoromethyl (—CF₃) provided that R₁is hydrogen; R₅ is hydrogen (—H), chlorine (—Cl), or fluorine (—F) atom,or group comprised of methyl (—CH₃), ethyl (—CH₂CH₃), ethylene (—CHCH₂),ethyne (—CCH), n-propyl (—CH₂CH₂CH₃), iso-propyl (—CH(CH₃)₂),cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃), propene (—CHCHCH₃ or—CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂), propyne (—CCCH₃ or—CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH), ethylalcohol(—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)), propanol(—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F), perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl); R₆ is hydrogen (—H), chlorine (—Cl), orfluorine (—F) atom, or group comprised of methyl (—CH₃), ethyl(—CH₂CH₃), ethylene (—CHCH₂), ethyne (—CCH), n-propyl (—CH₂CH₂CH₃),iso-propyl (—CH(CH₃)₂), cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃),propene (—CHCHCH₃ or —CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂),propyne (—CCCH₃ or —CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH),ethylalcohol (—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)),propanol (—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F), perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl); R₇ is hydrogen (—H), chlorine (—Cl), orfluorine (—F) atom, or group comprised of methyl (—CH₃), ethyl(—CH₂CH₃), ethylene (—CHCH₂), ethyne (—CCH), n-propyl (—CH₂CH₂CH₃),iso-propyl (—CH(CH₃)₂), cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃),propene (—CHCHCH₃ or —CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂),Propyne (—CCCH₃ or —CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH),ethylalcohol (—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)),propanol (—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F), perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or -CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl); R₈ is hydrogen (—H), chlorine (—Cl), orfluorine (—F) atom, or group comprised of methyl (—CH₃), ethyl(—CH₂CH₃), ethylene (—CHCH₂), ethyne (—CCH), n-propyl (—CH₂CH₂CH₃),iso-propyl (—CH(CH₃)₂), cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃),propene (—CHCHCH₃ or —CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂),propyne (—CCCH₃ or —CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH),ethylalcohol (—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)),propanol (—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F), perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl); R₉ is hydrogen (—H), chlorine (—Cl), orfluorine (—F) atom, or group comprised of methyl (—CH₃), ethyl(—CH₂CH₃), ethylene (—CHCH₂), ethyne (—CCH), n-propyl (—CH₂CH₂CH₃),iso-propyl (—CH(CH₃)₂), cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃),propene (—CHCHCH₃ or —CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂),propyne (—CCCH₃ or —CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH),ethylalcohol (—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)),propanol (—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F), perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl); and R₁₀ is hydrogen (—H), chlorine (—Cl), orfluorine (—F) atom, or group comprised of methyl (—CH₃), ethyl(—CH₂CH₃), ethylene (—CHCH₂), ethyne (—CCH), n-propyl (—CH₂CH₂CH₃),iso-propyl (—CH(CH₃)₂), cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃),propene (—CHCHCH₃ or —CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂),propyne (—CCCH₃ or —CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH),ethylalcohol (—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)),propanol (—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F), perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or -CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl).
 5. A compound of the formula:

wherein: R₁ is hydrogen (—H), methyl (—CH₃), or trifluoromethyl (—CF₃);R₂ is hydrogen; R₃ is hydrogen; R₄ is hydrogen, or methyl (—CH₃)provided that R₁ is hydrogen, or trifluoromethyl (—CF₃) provided that R₁is hydrogen; and wherein x and y are carbon atoms in the substituentformulas A, B, or C that are bonded to the same carbon atom as R₅ andR₆, respectively through the bonds indicated by dashed lines;

and wherein y and z are carbon atoms in the substituent formulas A′, B′,or C′ that are bonded to the same carbon atom as R₅ and R₆, respectivelythrough the bonds indicated by dashed lines;

And wherein; R₅, R₆, R₇, R₈, R₉, R₁₀, R₅′, R₆′, R₇′, R₈′, R₉′, and R₁₀′may independently be hydrogen (—H), chlorine (—Cl), or fluorine (—F)atom, or group comprised of methyl (—CH₃), ethyl (—CH₂CH₃), ethylene(—CHCH₂), ethyne (—CCH), n-propyl (—CH₂CH₂CH₃), iso-propyl (—CH(CH₃)₂),cyclopropyl (—CH(CH₂)₂), tert-butyl (—C(CH₃)₃), propene (—CHCHCH₃ or—CH₂CHCH₂), cyclopropene (—CH(CH)₂ or —C(CH)CH₂), propyne (—CCCH₃ or—CH₂CCH), hydroxyl (—OH), methylalcohol (—CH₂OH), ethylalcohol(—CH₂CH₂OH or —CH(OH)CH₃), ethyldiol (—CH(OH)CH₂(OH)), propanol(—CH(OH)CH₂CH₃ or —CH₂CH(OH)CH₃ or —CH₂CH₂CH₂OH), propandiol(—CH(OH)CH(OH)CH₃ or —CH(OH)CH₂CH₂OH or —CH₂CH(OH)CH₂OH), methylether(—OCH₃), ethylether (—OCH₂CH₃), fluoromethyl (—CH₂F), difluoromethyl(—CHF₂), trifluoromethyl (—CF₃), fluoroethyl (—CFHCH₃ or —CH₂CH₂F),perfluoroethyl (—CF₂CF₃), fluoropropyl (—CHFCH₂CH₃ or —CH₂CHFCH₃ or—CH₂CH₂CH₂F), perfluoropropyl (—CF₂CF₂CF₃ or —CF(CF₂)₂), chloromethyl(—CH₂Cl), dichloromethyl (—CHCl₂), trichloromethyl (—CCl₃), chloroethyl(—CClHCH₃ or —CH₂CH₂Cl), perchloroethyl (—CCl₂CCl₃), chloropropyl(—CHClCH₂CH₃ or —CH₂CHClCH₃ or —CH₂CH₂CH₂Cl), perchloropropyl(—CCl₂CCl₂CCl₃ or —CCl(CCl₂)₂), cyano (—CN), aldehyde (—C(O)H),carboxylic acid (—C(O)OH), carboxylate (—C(O)O⁻), carbomethoxy(—C(O)OCH₃), carboethoxy (—C(O)OCH₂CH₃), dimethyl amine (—N(CH₃)₂), oracid chloride (—C(O)Cl).
 6. A method of inhibiting the ethylene responsein a plant, said method comprising: a. A compound that upon exposure tolight releases 1-methylcyclopropene or a chemical analogue of1-methylcyclopropene and at least one additional linked molecule; and b.exposure of said compound to light in the presence of said plant.
 7. Themethod of inhibiting the ethylene response in a plant of claim 6 whereinsaid compound is a chemical analogue of 2(5H)-furanone.
 8. The method ofinhibiting the ethylene response in a plant of claim 6 wherein saidcompound is a methyl-2(5H)-furanone or a trifluoromethyl-2(5H)-furanone.9. The method of inhibiting the ethylene response in a plant of claim 6wherein said compound is a chemical analogue of 2(3H)-furanone.
 10. Themethod of inhibiting the ethylene response in a plant of claim 6 whereinsaid compound is a methyl-2(3H)-furanone or atrifluoromethyl-2(3H)-furanone.
 11. The method of inhibiting theethylene response in a plant of claim 6 wherein said compound is achemical analogue of 3-oxabicyclo[3.1.0]hexa-2,4-dione.
 12. The methodof inhibiting the ethylene response in a plant of claim 6 wherein saidcompound is 1-methyl-3-oxabicyclo[3.1.0]hexa-2,4-dione or1-trifluoromethyl-3-oxabicyclo[3.1.0]hexa-2,4-dione.
 13. The methodinhibiting the ethylene response in a plant of claim 6 wherein saidcompound is a chemical analogue of 2-oxa-bicyclo[2.1.0]penta-3-one. 14.The method of inhibiting the ethylene response in a plant of claim 6wherein said compound is 2 oxa-1-methyl-bicyclo[2.1.0]penta-3-one,3-oxa-1-methyl-bicyclo[2.1.0]penta-2-one,2-oxa-1-trifluoromethyl-bicyclo[2.1.0]penta-3-one, or3-oxa-1-trifluoromethyl-bicyclo[2.1.0]penta-2-one.
 15. The methodinhibiting the ethylene response in a plant of claim 6 wherein saidcompound is a chemical analogue of3,4-dioxa-bicyclo[4.1.0]hepta-2,5-dione.
 16. The method of inhibitingthe ethylene response in a plant of claim 6 wherein said compound is3,4-dioxa-1-methyl-bicyclo[4.1.0]hepta-2,5-dione or3,4-dioxa-1-trifluoromethyl-bicyclo[4.1.0]hepta-2,5-dione.
 17. Themethod of inhibiting the ethylene response in a plant of claim 6 whereinsaid compound is a chemical analogue oftetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-one.
 18. The method ofinhibiting the ethylene response in a plant of claim 6 wherein saidcompound is2-carbomethoxy-3-methyl-tetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-one;2-carbomethoxy-3-trifluoromethyl-tetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-one;2-carbomethoxy-5-methyl-tetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-one;2-carbomethoxy-5-trifluoromethyl-tetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-one;2,6-dicarbomethoxy-3-trifluoromethyl-tetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-one;or 2,6-dicarbomethoxy-3 -methyl-tetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-one.
 19. The method ofinhibiting the ethylene response in a plant of claim 17 wherein at leastone said additional linked molecule released upon the exposure of saidcompound to light is a fertilizer, pesticide, herbicide, fungicide,preservative, bee attractant or insect repellent.
 20. The method ofinhibiting the ethylene response in a plant of claim 6 wherein saidcompound is a chemical analogue oftricyclo[3.2.2.0^(2,4)]nona-6,8-diene.
 21. The method of inhibiting theethylene response in a plant of claim 6 wherein said compound is1-carbomethoxy-2-methyl-tricyclo[3.2.2.0^(2,4)]nona-6,8-diene;1-carbomethoxy-4-methyl-tricyclo[3.2.2.0^(2,4)]nona-6,8-diene;1-carbomethoxy-4-trifluoromethyl-tricyclo[3.2.2.0^(2,4)]nona-6,8-diene;1,5-dicarbomethoxy-2-methyl-tricyclo[3.2.2.0^(2,4)]nona-6,8-diene;1,5-dicarbomethoxy-2-trifluoromethyl-tricyclo[3.2.2.0^(2,4)]nona-6,8-diene;or1-carbomethoxy-2-trifluoromethyl-tricyclo[3.2.2.0^(2,4)]nona-6,8-diene.22. The method of inhibiting the ethylene response in a plant of claim20 wherein at least one said additional linked molecule released uponthe exposure of said compound to light is a fertilizer, pesticide,herbicide, fungicide, preservative, bee attractant or insect repellent.23. A method of inhibiting the ethylene response in a plant, said methodcomprising: a. A compound that upon exposure to heat releases1-methylcyclopropene or a chemical analogue of 1-methylcyclopropene andat least one additional linked molecule; and b. exposure of saidcompound to heat in the presence of said plant.
 24. The method ofinhibiting the ethylene response in a plant of claim 23 wherein saidcompound is a chemical analogue of 2-oxa-bicyclo[2.1.0]penta-3-one. 25.The method of inhibiting the ethylene response in a plant of claim 23wherein said compound is 1-methyl-2-oxa-bicyclo[2.1.0]penta-3-one;4-methyl-2-oxa-bicyclo[2.1.0]penta-3-one;1-trifluoromethyl-2-oxa-bicyclo[2.1.0]penta-3-one; or4-trifluoromethyl-2-oxa-bicyclo[2.1.0]penta-3-one.
 26. The method ofinhibiting the ethylene response in a plant of claim 23 wherein saidcompound is a chemical analogue of3,4-dioxa-bicyclo[4.1.0]hepta-2,5-dione.
 27. The method of inhibitingthe ethylene response in a plant of claim 23 wherein said compound is1-methyl-3,4-dioxa-bicyclo[4.1.0]hepta-2,5-dione or1-trifluoromethyl-bicyclo[4.1.0]hepta-2,5-dione.
 28. The method ofinhibiting the ethylene response in a plant of claim 23 wherein saidcompound is a chemical analogue oftetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10one.
 29. The method ofinhibiting the ethylene response in a plant of claim 23 wherein saidcompound is2-carbomethoxy-3-methyl-tetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-one;2-carbomethoxy-3-trifluoromethyl-tetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-one;2-carbomethoxy-5-methyl-tetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-one;2-carbomethoxy-5-trifluoromethyl-tetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-one;2,6-dicarbomethoxy-3-trifluoromethyl-tetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-one;or2,6-dicarbomethoxy-3-methyl-tetracyclo[5.2.1.0^(2,6).0^(3,5)]deca-8-en-10-one.30. The method of inhibiting the ethylene response in a plant of claim28 wherein at least one said additional linked molecule released uponthe exposure of said compound to light is a fertilizer, pesticide,herbicide, fungicide, preservative, bee attractant or insect repellent.31. The method of inhibiting the ethylene response in a plant of claim23 wherein said compound is a chemical analogue oftricyclo[3.2.2.0^(2,4)]nona-6,8-diene.
 32. The method of inhibiting theethylene response in a plant of claim 23 wherein said compound is1-carbomethoxy-2-methyl-tricyclo[3.2.2.0^(2,4)]nona-6,8-diene;1-carbomethoxy-4-methyl-tricyclo[3.2.2.0^(2,4)]nona-6,8-diene;1-carbomethoxy-4-trifluoromethyl-tricyclo[3.2.2.0^(2,4)]nona-6,8-diene;1,5-dicarbomethoxy-2-methyl-tricyclo[3.2.2.0^(2,4)]nona-6,8-diene;1,5-dicarbomethoxy-2-trifluoromethyl-tricyclo[3.2.2.0^(2,4)]nona-6,8-diene;or1-carbomethoxy-2-trifluoromethyl-tricyclo[3.2.2.0^(2,4)]nona-6,8-diene.33. The method of inhibiting the ethylene response in a plant of claim31 wherein at least one said additional linked molecule released uponthe exposure of said compound to light is a fertilizer, pesticide,herbicide, fungicide, preservative, bee attractant or insect repellent.34. The method of inhibiting the ethylene response in a plant of claim 6wherein said compound is additionally exposed to an acidic aqueoussolution.
 35. The method of inhibiting the ethylene response in a plantof claim 34 wherein said compound is a analogue of2-oxa-bicyclo[2.1.0]penta-3-one ketal.
 36. The method of inhibiting theethylene response in a plant of claim 34 wherein said compound is1-methyl-2-oxa-bicyclo[2.1.0]penta-3-one ketal;4-methyl-2-oxa-bicyclo[4.1.0]penta-3-one ketal;1-trifluoromethyl-2-oxa-bicyclo[2.1.0]penta-3-one ketal; or4-trifluoromethyl-2-oxa-bicyclo[2.1.0]penta-3-one ketal.